The polymer binders used in most lithium-ion batteries (LIBs) serve only a structural role, but there are exciting opportunities to increase performance by using polymers with combined electronic and ionic conductivity. To this end, here we examine dihexyl-substituted poly­(3,4-propylenedioxythiophene) (PProDOT-Hx2) as an electrochemically stable π-conjugated polymer that becomes electrically conductive (up to 0.1 S cm–1) upon electrochemical doping in the potential range of 3.2 to 4.5 V (vs Li/Li+). Because this family of polymers is easy to functionalize, can be effectively fabricated into electrodes, and shows mixed electronic and ionic conductivity, PProDOT-Hx2 shows promise for replacing the insulating polyvinylidene fluoride (PVDF) commonly used in commercial LIBs. A combined experimental and theoretical study is presented here to establish the fundamental mixed ionic and electronic conductivity of PProDOT-Hx2. Electrochemical kinetics and electron spin resonance are first used to verify that the polymer can be readily electrochemically doped and is chemically stable in a potential range of interest for most cathode materials. A novel impedance method is then used to directly follow the evolution of both the electronic and ionic conductivity as a function of potential. Both values increase with electrochemical doping and stay high across the potential range of interest. A combination of optical ellipsometry and grazing incidence wide angle X-ray scattering is used to characterize both solvent swelling and structural changes that occur during electrochemical doping. These experimental results are used to calibrate molecular dynamics simulations, which show improved ionic conductivity upon solvent swelling. Simulations further attribute the improved ionic conductivity of PProDOT-Hx2 to its open morphology and the increased solvation is possible because of the oxygen-containing propylenedioxythiophene backbone. Finally, the performance of PProDOT-Hx2 as a conductive binder for the well-known cathode LiNi0.8Co0.15Al0.05O2 relative to PVDF is presented. PProDOT-Hx2-based cells display a fivefold increase in capacity at high rates of discharge compared to PVDF-based electrodes at high rates and also show improved long-term cycling stability. The increased rate capability and cycling stability demonstrate the benefits of using binders such as PProDOT-Hx2, which show good electronic and ionic conductivity, combined with electrochemical stability over the potential range for standard cathode operation.

Mixed electron- and ion-conducting polymers serve as excellent candidates for polymer binders in lithium-ion batteries (LIBs) because of an extension of functionality beyond simple mechanical adhesion. Such dual conduction was observed in our recent report on dihexyl-substituted poly­(3,4-propylenedioxythiophene) (PProDOT-Hx2), which showed excellent performance as a cathode binder for LiNi0.8Co0.15Al0.05O2 (NCA). However, ionic conductivity was found to be significantly lower than that of its electronic counterpart. To enhance mixed conduction, here we report a family of synthetically tunable, electrochemically stable, random copolymers based on PProDOT-Hx2, in which the hexyl (Hex) side chains are replaced to varying extents with oligoether (OE) side chains, generating a series of (Hex:OE) PProDOTs. When OE content was varied from 5 to 35%, the resulting copolymers were insoluble in the battery electrolyte and were stable after 100 electrochemical doping/dedoping cycles. Electron paramagnetic resonance and electrochemical kinetics studies were performed to illustrate the reversible and fast electrochemical doping process of (Hex:OE) PProDOTs. Electronic and ionic conductivity measurements as a function of electrochemical potential show a decrease in electronic conductivity and a concurrent increase in ionic conductivity with increasing incorporation of OE side chains. X-ray scattering studies on electrochemically doped polymers indicate a decline in crystalline ordering with the increase in OE content of the (Hex:OE) PProDOTs, suggesting that decreasing crystallinity is responsible for both the increased ionic and reduced electronic conductivity. Compounding these structural changes, swelling studies show a linear mass increase with OE content upon electrolyte exposure, indicating that solvent-induced swelling and electrolyte uptake play a significant role in the ability of these polymers to conduct ions. Finally, rigorous cell testing was performed by employing electrochemical impedance spectroscopy, galvanostatic charge–discharge, rate capability tests, and differential capacity vs voltage analysis, using NCA cathodes to understand the role of these polymers as mixed electron- and Li+-ion-conducting polymer binders in LIBs in comparison to the commonly used polyvinylidene fluoride. It is observed that (75:25) PProDOT containing 25% of OE side chains achieves the highest rate capability and fastest charging and discharging under symmetric testing conditions. The synthetic flexibility to fine-tune electronic and ionic conductivity makes (Hex:OE) PProDOTs a promising new class of mixed conducting polymers for electrochemical energy-storage application.

Conductive polymers are being studied increasingly as additives in lithium-ion batteries, supercapacitors, and other electrochemical devices due to their ability to conduct electrons and ions and serve as binders. These polymers undergo electrochemical doping during battery cycling along with swelling by the electrolyte solvent, whereupon the ionic and electronic conductivities change by several orders of magnitude. Measuring these large changes as a function of electrochemical doping, in situ, in a relevant electrolyte, has been a challenge thus far. We show that the ionic and electronic conductivity of a range of p-type and n-type conducting polymer thin films can be reliably measured as a function of electrochemical doping in relevant battery electrolytes by impedance spectroscopy on interdigitated electrodes by combining two separate electrode geometries. The results demonstrate the broad applicability of the methodology for gaining insights into the electrical conduction in polymers in relevant environments, particularly for batteries and other electrochemical devices.

We define fuzzy sets on the Hough transform of character pattern pixels from which additional fuzzy sets are synthesized using t-norms. A multilayer perceptron trained with a number of linguistic set memberships derived from these t-norms can recognize characters of Bengali scripts by theirsimilarities to different fuzzy pattern classes.

A broad family of ductile semirandom donor− acceptor (D−A) copolymers with 8-carbon alkyl conjugation break spacer (CBS) units were incorporated into ternary blend organic solar cells in order to determine their impact on the electrical metrics of solar cell performance. The goal of this study was to elucidate potential co-optimization strategies for photovoltaic and mechanical properties in organic solar cells. The ternary blended active layers were based on two polymer donors and the acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM). In all cases, the majority polymer donor component was the previously reported fully conjugated semirandom polymer P3HTT-ehDPP-10%, comprised of 80% 3-hexylthiophene, 10% diketopyrrolopyrrole (DPP) with 2-ethylhexyl (eh) side chains, and 10% thiophene. As the second donor, three different classes of CBS polymers were used, where the spacer length was kept constant at 8 methylene units. The mechanical properties of these polymers are quite notable with moduli as low as 8.54 MPa and fracture strains as high as 432%. However, it was found that as ductility increased, hole mobility decreased. In this study, we observed that the hole mobilities of the ternary active layers generally increased upon increasing the content of the CBS polymer up to 15% of the overall donor fraction. The higher carrier mobilities likely contribute to the higher J SC observed in many of the ternary devices. The as-cast ternary solar cells made in ambient environment without any pre/post treatment gave strong performance up to 25% of CBS polymer loading. This work demonstrates that introducing highly stretchable CBS polymers with poor charge mobility does not adversely affect solar cell performance, offering insights into the development of ternary strategies for flexible/stretchable organic solar cells.